JP6956086B2 - Cobalt-containing film-forming compositions, their synthesis and use in film precipitation - Google Patents

Description

Cross-references to related applications Benefits of U.S. Patent Application No. 14 / 986,286, filed December 31, 2015, which is incorporated herein by reference in its entirety for all purposes. To charge.

Cobalt-containing film-forming compositions, their preparation and their use for vapor deposition of films are disclosed. The cobalt-containing film-forming composition comprises a silylamide-containing precursor, in particular Co [N (SiMe ₃ ) ₂ ] ₂ (NMe ₂ Et) and / or Co [N (SiMe ₃ ) ₂ ] ₂ (NMeEt ₂ ). Become.

Chemical vapor deposition (CVD) and atomic layer deposition (ALD) have been applied as major deposition techniques for producing thin films for semiconductor devices. These methods allow the achievement of conformal films (metals, oxides, nitrides, silicides, etc.) by finely adjusting the parameters between the precipitation processes. Primarily film growth is controlled by chemical reactions of metal-containing compounds (precursors), and the development of optimal precursors is essential in anticipation of their properties and reaction process.

In particular, films of transition metals and transition metal silicides of manganese, iron, cobalt and ruthenium have become important for a variety of electronic and electrochemical applications. Cobalt thin films , for example, are interesting because of their high magnetic permeability. There are many reports that cobalt thin films are used to form _{cobalt disilicate (CoSi 2} ) in the front-end process of semiconductor devices due to their low resistance to ohm contact. Cobalt-containing thin films have recently been investigated as Cu / low k barriers, passivation layers and capping layers for very large integrated devices.

Synthesis of silylamide compounds has been reported (Monash. Chem. (1963), 94 (6), pp. 1007-1012; Polyhedron 22 (2003) pp. 67-73, JCS Chem. Comm. ( 1972) pp. 872-873; Inorgan. Chem. (1984) 23,4584-4588; US Pat. No. 6,695,039 B2). Thin-film film formation using silylamide compounds has also been reported (Chem. Vap. Deposition 1995, 1, No. 2, 49-51; RG Gordon et al .; Applied Materials, US Patent Application Publication No. 2009/0053426A1. US Patent Application Publication No. 2014/0255606, Applied Materials).

US Pat. No. 6,969,539 to Gordon et al. Discloses:

Those skilled in the art will recognize that the liquid form of the Co-containing precursor is preferred for deposition methods and the disclosed vapor pressure is very low for industrial use for thin film precipitation.

Choosing a Co-containing precursor that volatilizes properly while remaining stable enough for use in vapor phase film precipitation is important for commercial practice and is not always easily determined.

The following formula:

(In the formula, M is Co; each R ¹ , R ² and R ³ is independently selected from hydrogen (H) or C1-C4 hydrocarbons; L is pyridine, NMe ₃ , NEt ₃ , One or two neutral adducts selected from NMe ₂ Et, _{NMe Et 2} , 1-Me-pyrrolidine or PMe ₃ ^{; and R 1} and R ² or R ² and R ³ are attached to the ring. A cobalt-containing film-forming composition comprising a silylamide-containing precursor having a (may form a silicon-containing heterocycle) is disclosed. The disclosed silylamide-containing film-forming composition may have one or more of the following embodiments:
● Each R ¹ , R ² and R ³ is independently selected from H, methyl, ethyl, isopropyl, n-propyl, n-butyl or t-butyl;
● The silylamide-containing precursor is {Co [N (SiMe ₃ ) ₂ ] ₂ } ₂ ;
● The silylamide-containing precursor is Co [N (SiMe ₃ ) ₂ ] ₂ (py);
● The silylamide-containing precursor is Co [N (SiMe ₃ ) ₂ ] ₂ (Me ₃ N);
● The silylamide-containing precursor is Co [N (SiMe ₃ ) ₂ ] ₂ (Et ₃ N);
● The silylamide-containing precursor is Co [N (SiMe ₃ ) ₂ ] ₂ (Me ₂ EtN);
● The silylamide-containing precursor is Co [N (SiMe ₃ ) ₂ ] ₂ (MeEt ₂ N);
● The silylamide-containing precursor is Co [N (SiMe ₃ ) ₂ ] ₂ (1-Me-pyrrolidine);
● The silylamide-containing precursor is Co [N (SiMe ₃ ) ₂ ] ₂ (PMe ₃ );
● The silylamide-containing precursor is {Co [N (SiMe ₂ Et) ₂ ] ₂ } ₂ ;
● The silylamide-containing precursor is Co [N (SiMe ₂ Et) ₂ ] ₂ (py);
● The silylamide-containing precursor is Co [N (SiMe ₂ Et) ₂ ] ₂ (Me ₃ N);
● The silylamide-containing precursor is Co [N (SiMe ₂ Et) ₂ ] ₂ (Et ₃ N);
● The silylamide-containing precursor is Co [N (SiMe ₂ Et) ₂ ] ₂ (Me ₂ EtN);
● The silylamide-containing precursor is Co [N (SiMe ₂ Et) ₂ ] ₂ (MeEt ₂ N);
● The silylamide-containing precursor is Co [N (SiMe ₂ Et) ₂ ] ₂ (1-Me-pyrrolidine);
● The silylamide-containing precursor is Co [N (SiMe ₂ Et) ₂ ] ₂ (PMe ₃ );
● The cobalt-containing film-forming composition comprises from about 99% w / w to about 100% w / w of silylamide-containing precursors;
● The cobalt-containing film-forming composition comprises a silylamide-containing precursor of about 99% w / w to about 100% w / w after 4 weeks at 50 ° C .;
● The cobalt-containing film-forming composition comprises a silylamide-containing precursor of about 99% w / w to about 100% w / w after 12 weeks at room temperature (about 23 ° C.);
● Cobalt-containing film-forming compositions yield less than 3% residual mass under thermogravimetric analysis after a 2-week stability test at temperatures producing vapor pressure of 1 torr of silylamide-containing precursors;
● Cobalt-containing film-forming compositions yield less than 3% residual mass under thermogravimetric analysis after a 3-week stability test at temperatures producing vapor pressure of 1 torr of silylamide-containing precursors;
● Cobalt-containing film-forming compositions yield less than 3% residual mass under thermogravimetric analysis after a 2-month stability test at temperatures producing vapor pressure of 1 torr of silylamide-containing precursors;
● The cobalt-containing film-forming composition comprises from about 95% w / w to about 100% w / w of silylamide-containing precursors;
● The Co-containing film-forming composition comprises from about 5% w / w to about 50% w / w of silylamide-containing precursors;
● The Co-containing film-forming composition does not contain water;
● The Co-containing film-forming composition comprises impurities of about 0% w / w to about 5% w / w;
● The Co-containing film-forming composition comprises impurities of about 0.0% w / w to about 2.0% w / w;
● The Co-containing film-forming composition comprises impurities of about 0.0% w / w to about 1.0% w / w;
● Halides include halides, alkali metals, allyl-substituted silanes, lithium, sodium or potassium halides; THF; ethers; pentane; cyclohexane; heptane; benzene; toluene;
● The Co-containing film-forming composition comprises from about 0 ppbw to about 1 ppmw of metal impurities;
● The Co-containing film-forming composition comprises from about 0 ppbw to about 500 ppbb of metal impurities;
● The Co-containing film-forming composition comprises from about 0 ppbb to about 100 ppbb of Al;
● The Co-containing film-forming composition comprises from about 0 ppbb to about 100 ppbb of As;
● The Co-containing film-forming composition comprises from about 0 ppbb to about 100 ppbb Ba;
● The Co-containing film-forming composition comprises from about 0 ppbb to about 100 ppbb of Be;
● The Co-containing film-forming composition comprises from about 0 ppbb to about 100 ppbb of Bi;
● The Co-containing film-forming composition comprises from about 0 ppbb to about 100 ppbb of Cd;
● The Co-containing film-forming composition comprises from about 0 ppbb to about 100 ppbb of Ca;
● The Co-containing film-forming composition comprises about 0 ppbb to about 100 ppbb of Cr;
● The Co-containing film-forming composition comprises from about 0 ppbb to about 100 ppbb of Cu;
● The Co-containing film-forming composition comprises from about 0 ppbb to about 100 ppbb of Ga;
● The Co-containing film-forming composition comprises from about 0 ppbb to about 100 ppbb of Ge;
● The Co-containing film-forming composition comprises from about 0 ppbb to about 100 ppbb of Hf;
● The Co-containing film-forming composition comprises from about 0 ppbb to about 100 ppbb of Zr;
● The Co-containing film-forming composition comprises from about 0 ppbb to about 100 ppbb of In;
● The Co-containing film-forming composition comprises from about 0 ppbb to about 100 ppbb of Fe;
● The Co-containing film-forming composition comprises from about 0 ppbw to about 100 ppbw of Pb;
● The Co-containing film-forming composition comprises from about 0 ppbb to about 100 ppbb of Li;
● The Co-containing film-forming composition comprises from about 0 ppbb to about 100 ppbb of Mg;
● The Co-containing film-forming composition comprises about 0 ppbb to about 100 ppbb of Mn;
● The Co-containing film-forming composition comprises from about 0 ppbb to about 100 ppbb of W;
● The Co-containing film-forming composition comprises from about 0 ppbb to about 100 ppbb of Ni;
● The Co-containing film-forming composition comprises from about 0 ppbb to about 100 ppbb of K;
● The Co-containing film-forming composition comprises from about 0 ppbb to about 100 ppbb of Na;
● The Co-containing film-forming composition comprises from about 0 ppbb to about 100 ppbb of Sr;
● The Co-containing film-forming composition comprises from about 0 ppbb to about 100 ppbb of Th;
● The Co-containing film-forming composition comprises Sn of about 0 ppbb to about 100 ppbb;
● The Co-containing film-forming composition comprises from about 0 ppbb to about 100 ppbb of Ti;
● The Co-containing film-forming composition comprises from about 0 ppbb to about 100 ppbb of U;
● The Co-containing film-forming composition comprises V from about 0 ppbb to about 100 ppbb;
● The Co-containing film-forming composition comprises about 0 ppbb to about 100 ppbb of Zn;
● The Co-containing film-forming composition comprises from about 0 ppmw to about 100 ppmw of Cl;
● The Co-containing film-forming composition contains Br of about 0 ppmw to about 100 ppmw.

Also disclosed is a Co-containing film-forming composition delivery device comprising a canister with an inlet and outlet conduits and containing any of the Co-containing film-forming compositions disclosed above. The disclosed device may have one or more of the following aspects:
● The Co-containing film-forming composition has a total concentration of less than 10 ppmw of metal contaminants;
● the ends of the inlet conduits are disposed on the surface of the Co-containing film-forming composition, and the end of the outlet conduit is disposed below the surface of the Co-containing film-forming composition;
● the ends of the inlet conduits are arranged below the surface of the Co-containing film-forming composition, and the end of the outlet conduit is disposed on the surface of the Co-containing film-forming composition;
● Additional diaphragm valves on the inlet and outlet;
● One or more barrier layers may be further included on the inner surface of the canister;
● An additional 1 to 4 barrier layers are included on the inner surface of the canister;
● One or two additional barrier layers on the inner surface of the canister;
● Each barrier layer comprises a silicon oxide layer, a silicon nitride layer, a silicon nitride layer , a silicon nitride layer, a silicon nitride layer or a combination thereof;
● Each barrier layer is 1 to 100 nm thick;
● Each barrier layer is 2-10 nm thick;
● The Co-containing film-forming composition comprises Co [N (SiMe ₃ ) ₂ ] ₂ (NMe ₂ Et);
● The Co-containing film-forming composition comprises Co [N (SiMe ₃ ) ₂ ] ₂ (NMeEt ₂ ).

Also disclosed is a method of precipitating a Co-containing layer on a substrate. The vapor of any of the Co-containing film-forming compositions disclosed above is introduced into a reactor in which a substrate is placed. A vapor deposition method is used to precipitate at least a portion of the silylamide-containing precursor onto a substrate to form a Co-containing layer. The disclosed method may have one or more of the following aspects:
● The Co-containing film-forming composition is a silylamide-containing precursor selected from _{Co [N (SiMe 3} ) ₂ ] ₂ (NMe ₂ Et), Co [N (SiMe ₃ ) ₂ ] ₂ (NMeEt _{2), or a combination thereof.} Including;
● The silylamide-containing precursor is Co [N (SiMe ₃ ) ₂ ] ₂ (NMe ₂ Et);
● The silylamide-containing precursor is Co [N (SiMe ₃ ) ₂ ] ₂ (NMeEt ₂ );
● Introduce steam containing the second precursor into the reactor;
● elements of the second precursor, Group 2, Group 13, Group 14, transition metals, selected from the group consisting of lanthanum Roh id and combinations thereof;
● The elements of the second precursor are Mg, Ca, Sr, Ba, Zr, Hf, Ti, Nb, Ta,
Al, Si, Ge, selected from Y or lanthanide Roh id;
● Introduce the reactants into the reactor;
● Reactants are _{selected from the group consisting of O 2} , O ₃ , H ₂ O, H ₂ O ₂ , NO, NO ₂ , carboxylic acids, their radicals and combinations thereof;
● The reactant is plasma treated oxygen;
● The reactant is ozone;
● _{reactant, H 2, NH 3, (} SiH 3) 3 N, (SiH 4, Si 2 H 6, Si 3 H 8, Si 4 H 10, Si 5 H 10, Si , such as _{6 H 12)} hydride Silanes, _{chlorosilanes and chloropolysilanes (such as SiHCl 3} , SiH ₂ Cl ₂ , SiH ₃ Cl, Si ₂ Cl ₆ , Si ₂ HCl ₅ , Si ₃ Cl _8, etc.), (Me ₂ SiH ₂ , Et ₂ SiH ₂ , MeSiH _3). ) alkyl silanes such as _{EtSiH 3, (N 2 H 4} , MeHNNH 2, etc.) hydrazine MeHNNHMe, (such as ethanol or methanol) _{alcohol, (NMeH 2, NEtH 2,} NMe 2 H, NEt 2 H, NMe 3 , _{NEt 3,} (SiMe 3), such as ₂ NH) organic amines, pyrazoline, _{pyridine, (B 2} H _6, 9- borabicyclo [3,3,1] nonane, Torimechirubo Ron, triethyl boron, such as borazine) B-containing Selected from the group consisting of molecules, alkylmetals (such as trimethylaluminum, triethylaluminum, dimethylzinc, diethylzinc, etc.), their radical species and mixtures thereof;
● The reaction product is a _{group consisting of H 2} , NH ₃ , SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , SiH ₂ Me ₂ , SiH ₂ Et ₂ , N (SiH ₃ ) ₃ , hydrogen radicals thereof and a mixture thereof. Selected from;
● The reactants are NH ₃ , N ₂ H ₄ , N (SiH ₃ ) ₃ , N (CH ₃ ) H ₂ , N (C ₂ H ₅ ) H ₂ , N (CH ₃ ) ₂ H, N (C _2). H ₅ ) ₂ H, N (CH ₃ ) ₃ , N (C ₂ H ₅ ) ₃ , (SiMe ₃ ) ₂ NH, (CH ₃ ) HNNH ₂ , (CH ₃ ) ₂ NNH ₂ , its nitrogen-containing radical species and Selected from the group consisting of the mixture;
● The reactant is HCDS or PCDS;
● reactant be a plasma treatment N _2;
● The vapor deposition method is a chemical vapor deposition (CVD) process;
● The vapor deposition method is the ALD process;
● The vapor deposition method is the PEALD process;
● The deposition method is a spatial ALD process;
● The Co-containing layer is the cobalt oxide layer;
● The Co-containing layer is a cobalt nitride layer;
● The Co-containing layer is Co; and ● The Co-containing layer is CoSi.

Notation and Nomenclature Certain abbreviations, symbols and terms are used throughout the following items and claims and include:

As used herein, the indefinite article "a" or "an" means one or more.

As used herein, the term "approximate" or "about" means ± 10% of the specified value.

Any and all ranges described herein include their endpoints (ie, x = 1-4 includes any number in between x = 1, x = 4 and x =). ..

As used herein, the term "alkyl group" means a saturated functional group containing only carbon and hydrogen atoms. In addition, the term "alkyl group" means a linear, branched or cyclic alkyl group. Examples of the linear alkyl group include, but are not limited to, a methyl group, an ethyl group, a propyl group, a butyl group and the like. Examples of branched chain alkyl groups include, but are not limited to, t-butyl. Examples of the cyclic alkyl group include, but are not limited to, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group and the like.

As used herein, the term "hydrocarbon" means a functional group containing only hydrogen and carbon atoms. Functional groups may be saturated (containing only single bonds) or unsaturated (containing double or triple bonds).

As used herein, the term "heterocycle" means a cyclic compound having at least two different elemental atoms as its ring members.

As used herein, the abbreviation "Me" means a methyl group; the abbreviation "Et" means an ethyl group; the abbreviation "Pr" means any propyl group (ie, that is). (n-propyl or isopropyl); the abbreviation "iPr" means an isopropyl group; the abbreviation "Bu" means any butyl group (n-butyl, isobutyl, t-butyl, sec-butyl). The abbreviation "tBu" means a tert-butyl group; the abbreviation "sBu" means a sec-butyl group; the abbreviation "iBu" means an isobutyl group; "Ph" The abbreviation means phenyl group; the abbreviation "py" means pyridine group; the abbreviation "THF" means tetrahydrofuran; and the abbreviation "Cp" means cyclopentadienyl group. do.

In the present specification, standard abbreviations for elements from the Periodic Table of Elements are used. It should be understood that the element may be indicated by these abbreviations (eg, Co means cobalt, Si means silicon, C means carbon, etc.).

Note that films or layers such as cobalt oxide are listed throughout the specification and claims without reference to their appropriate stoichiometry. Layer, M is located in Co; and k, l, m, n, o and p is in a range of comprehensive 1-6, pure (M) layer, silicide _(M o Si _p) layer, It may contain a carbide (M _o C _p ) layer, a nitride (M _k N _l ) layer, an oxide (M _n O _m ) layer or a mixture thereof. For example, cobalt silicide is, k and l are each in the range of 0.5 to 5, a _Co k Si _l. Similarly, _Co n _{O m} may include CoO and _Co 3 _{O 4.} None of the referenced layer, n is in the range of 0.5 to 1.5, and m is in the range of 1.5 to 3.5, silicon oxide layer, may comprise a _Si n _{O m.} More preferably, the silicon oxide layer is SiO ₂ . Silicon oxide layers are available from Applied Materials, Inc. It may be a silicon oxide-based dielectric material such as a carbon-doped silicon oxide-based low-k dielectric material such as the Black Diamond II or III material according to. Alternatively, any referenced silicon-containing layer may be pure silicon. Any silicon-containing layer may contain dopants such as B, C, P, As and / or Ge.

To further understand the nature and purpose of the invention, the following detailed description should be referred to along with the accompanying drawings. In the accompanying drawings, similar elements are given the same or similar reference numbers.

FIG. 5 is a side sectional view of an embodiment of a Co-containing film forming composition delivery device 1. FIG. 5 is a side sectional view of a second embodiment of a Co-containing film forming composition delivery device 1. FIG. 5 is a side sectional view of an exemplary embodiment of a solid precursor sublimator 100 for sublimating a solid Co-containing film-forming composition. Co [N (SiMe ₃ ) ₂ ] ₂ (THF), Co [N (SiMe ₂ Et) ₂ ] ₂ (THF), Co [N (SiMe ₃ ) ₂ ] ₂ (py), Co [N (SiMe ₃ ) ₂ ] ₂ (NMe ₂ Et), Co [N (SiMe ₃ ) ₂ ] ₂ (NMeEt ₂ ), Co [N (SiMe ₃ ) ₂ ] ₂ (NET ₃ ), Co [N (SiMe ₃ ) ₂ ] ₂ (Me-pyrrolidin) and Co [N (SiMe ₂ Et) ₂ ] ₂ (NMe ₂ Et) weight loss percent, comparative open cup thermal weight analysis (TGA) graph under 1010 millibars. Co [N (SiMe ₂ Et) ₂ ] ₂ (THF), Co [N (SiMe ₃ ) ₂ ] ₂ (py), Co [N (SiMe ₃ ) ₂ ] ₂ (NMeEt ₂ ), Co [ N (SiMe ₃ ) ₂ ] ₂ (NET ₃ ), Co [N (SiMe ₃ ) ₂ ] ₂ (Me-pyrrolidine) and Co [N (SiMe ₂ Et) ₂ ] ₂ (NMe ₂ Et) weight loss percent Shown, comparative open cup TGA graph under 20 millibars. Comparative TGA graph showing the percent weight loss _{of Co [N (SiMe 3} ) ₂ ] ₂ (py) due to increased temperature before and after the stability test at 150 ° C. Shows the percentage weight loss _{of Co [N (SiMe 3} ) ₂ ] _{2 (NMe 2} Et) due to increased temperature before and after 1, 2 and 3 weeks and 1 and 2 months of stability testing at 90 ° C. , Comparison TGA graph. Comparative TGA graph showing the percent weight loss _{of Co [N (SiMe 3} ) ₂ ] ₂ (NMeEt ₂ ) due to increased temperature before and after 1, 2 and 3 weeks of stability testing at 80 ° C. Comparative TGA graph showing the percent weight loss _{of Co [N (SiMe 3} ) ₂ ] ₂ (1-Me-pyrrolidin) due to increased temperature before and after 1 and 2 weeks of stability testing at 110 ° C. Comparative TGA graph showing the percent weight loss _{of Co [N (SiMe 2} Et) ₂ ] ₂ (NMe ₂ Et) due to increased temperature before and after 1 and 2 weeks of stability testing at 120 ° C.

The following formula:

(In the formula, M is Co; each R ¹ , R ² and R ³ is independently selected from hydrogen (H) or C1-C4 hydrocarbons; L is pyridine, NMe ₃ , NEt ₃ , One or two neutral adducts selected from NMe ₂ Et, _{NMe Et 2} , 1-Me-pyrrolidine or PMe ₃ ^{; and R 1} and R ² or R ² and R ³ are attached to the ring. A Co-containing film-forming composition comprising a silylamide-containing precursor having a (may form a silicon-containing heterocycle) is disclosed. Each R ¹ , R ² and R ³ is preferably independently methyl, ethyl, isopropyl, n-propyl, n-butyl or t-butyl.

Exemplary silylamide-containing precursors with formula I include Co [N (SiMe ₃ ) ₂ ] ₂ (py); Co [N (SiMe ₃ ) ₂ ] ₂ (Me ₃ N); Co [N (SiMe _3). ) ₂ ] ₂ (Et ₃ N); Co [N (SiMe ₃ ) ₂ ] ₂ (Me ₂ EtN); Co [N (SiMe ₃ ) ₂ ] ₂ (MeEt ₂ N); Co [N (SiMe ₃ ) ₂ ] ₂ (1-Me-pyrrolidin); Co [N (SiMe ₃ ) ₂ ] ₂ (PMe ₃ ); Co [N (SiMe ₂ Et) ₂ ] ₂ (py); Co [N (SiMe ₂ Et) ₂ ] ₂ (Me ₃ N); Co [N (SiMe ₂ Et) ₂ ] ₂ (Et ₃ N); Co [N (SiMe ₂ Et) ₂ ] ₂ (Me ₂ EtN); Co [N (SiMe ₂ Et) ₂ ] ₂ (MeEt ₂ N); Co [N (SiMe ₂ Et) ₂ ] ₂ (1-Me-pyrrolidin); Co [N (SiMe ₂ Et) ₂ ] ₂ (PMe ₃ ) and combinations thereof.

Illustrative silylamide-containing precursors having formula II include {Co [N (SiMe ₃ ) ₂ ] ₂ } ₂ ; {Co [N (SiMe ₂ Et) ₂ ] ₂ } ₂ and combinations thereof.

_{The silylamide-containing precursors are CoX 2 in} which X is Cl, Br or I and M in which M is Li, Na or K in a solvent such as tetrahydrofuran (THF), ether, pentane, cyclohexane, hexane, heptane or toluene. It can be synthesized by reacting with (N (SiR ¹ R ² R ³ ) _2). The solvent may be removed using filtration and / or sublimation, and the product of formula I or II may be isolated from the salt by-product. The L = THF adduct of formula I is replaced by adding the protonated form of the desired ligand to an alkane solution of the THF-containing precursor such as pentane, heptane, hexane or cyclohexane and extracting the product. You may. Further details are provided in the following examples.

To ensure process reliability, the disclosed Co-containing film-forming compositions are from about 95% w / w to about 100% w / w, preferably from about 98% w / w to about 100% w / w. It may be purified by continuous or fractional batch distillation, recrystallization, or sublimation prior to use to a range of purity. When the purity ranges from about 99% w / w to about 100% w / w, the Co-containing film-forming composition essentially consists of a silylamide-containing precursor. Those skilled in the art will recognize that the purity can be determined by 1 H NMR, or gas or liquid chromatography, along with mass spectrometry. Co-containing film-forming compositions may contain any of the following impurities: halides, alkali metals, alkylamines, alkylamino-substituted silanes, pyridines, 1-methylpyrrolidines, pyrrolidines, THFs, ethers, pentane, cyclohexanes, Heptane, toluene, metal halide compounds. Preferably, the total amount of impurities is less than 0.1% w / w. The purified composition can be prepared by passing a gas or liquid through a suitable adsorption medium such as recrystallization, sublimation, distillation and / or 4 Å molecular sieve.

The concentration of each solvent such as THF, ether, pentane, cyclohexane, heptane and / or toluene in the purified Co-containing film-forming composition is from about 0% w / w to about 5% w / w, preferably about 5% w / w. It may be in the range of about 0% w / w to about 0.1% w / w. The solvent may be used in the synthesis of Co-containing film-forming compositions. Separation of the solvent from the composition can be difficult if both have similar boiling points. Cooling the mixture can produce a solid precursor in a liquid solvent, which can be separated by filtration. Vacuum distillation may also be used if the composition is not heated approximately beyond its decomposition point.

The disclosed Co-containing film-forming compositions are less than 5% v / v, preferably less than 1% v / v, more preferably less than 0.1% v / v, and even more preferably 0.01. Contains any of its analogs or other reaction products less than% v / v. The present embodiment may provide better process reproducibility. The present embodiment can be produced by distillation of the Co-containing film-forming composition.

Alternatively, the disclosed Co-containing film-forming compositions can be from about 5% w / w, especially if the mixture provides improved process parameters or if the isolation of the target compound is very difficult or expensive. It may contain one compound of about 50% w / w and the rest of the composition will contain a second compound. For example, the disclosed Co-containing film-forming compositions are 40/60% w / w Co [N (SiMe ₃ ) ₂ ] ₂ (NMe ₂ Et) and Co [N (SiMe ₃ ) ₂ ] ₂ (NMeEt _2). ) Can be. The mixture can produce a stable liquid composition suitable for vapor deposition.

The concentrations of trace metals and metalloids in the purified Co-containing film-forming composition can independently be in the range of about 0 ppbw to about 100 ppbw, more preferably about 0 ppbw to about 10 ppbw. These metal or metalloid impurities include, but are not limited to, aluminum (Al), arsenic (As), barium (Ba), beryllium (Be), bismuth (Bi), cadmium (Cd), calcium (Ca), chromium ( Cr), copper (Cu), gallium (Ga), germanium (Ge), hafnium (Hf), zirconium (Zr), indium (In), iron (Fe), lead (Pb), lithium (Li), magnesium ( Mg), manganese (Mn), tungsten (W), nickel (Ni), potassium (K), sodium (Na), strontium (Sr), lithium (Th), tin (Sn),
Includes titanium (Ti), uranium (U), vanadium (V) and zinc (Zn). The concentration of X (X = Cl, Br) in the purified Co-containing film-forming composition can range from about 0 ppmw to about 100 ppmw, more preferably from about 0 ppmw to 10 ppmw.

Exposure to water of the disclosed Co-containing film-forming composition, since that may lead to degradation of Shiriruami de-containing precursors, it should be careful to interfere is.

Also disclosed is a method using the Co-containing film-forming composition disclosed for the vapor deposition method. The disclosed method provides the use of Co-containing film-forming compositions for precipitation of cobalt-containing films. The disclosed methods can be useful in the manufacture of semiconductors, photovoltaics, LCD-TFTs, flat panel devices, refractory materials or aviation components.

The disclosed methods for forming a cobalt-containing layer on a substrate are: placing the substrate in a reactor, delivering the vapor of the Co-containing film-forming composition disclosed in the reactor, and the vapor and the substrate. Includes contacting (and typically directing vapor towards the substrate) to form a cobalt-containing layer on the surface of the substrate.

This method is particularly, x is 1-4, and M is, Ti, Ta, Mn, Al, Koh Roh id (Er) or for the deposition of CoMn _x film combinations thereof, using a vapor deposition process It may include forming a dimetal-containing layer on the substrate. The disclosed methods can be useful in the manufacture of semiconductors, photovoltaics, LCD-TFTs or flat panel type devices. N ₂ , NH ₃ , hydrazine, amines, their N radicals and combinations thereof, but preferably _{H 2} or nitrogen sources such as _{NH 3} or plasma treated N ₂ may also be introduced into the reactor.

The disclosed Co-containing film-forming composition may be used to precipitate a cobalt-containing film using any of the precipitation methods known to those of skill in the art. Examples of suitable precipitation methods include chemical vapor deposition (CVD) or atomic layer deposition (ALD). Illustrative CVD methods include thermal CVD, pulsed CVD (PCVD), reduced pressure CVD (LPCVD), low atmospheric pressure CVD (SACVD) or atmospheric pressure CVD (APCVD), heat ray CVD (HWCVD, hot wire deposition process). Includes (also known as cat-CVD), which acts as an energy source), radical-involved CVD, plasma-enhanced CVD (PECVD), including, but not limited to, fluid PECVD, and combinations thereof. Exemplary ALD methods include thermal ALDs, plasma-enhanced ALDs (PEALDs), spatially isolated ALDs, heat ray ALDs (HWALDs), radical-involved ALDs and combinations thereof. Supercritical fluid precipitation may also be used. The precipitation method is preferably ALD, PE-ALD or spatial ALD in order to provide appropriate step coating and film thickness control.

The vapor of the Co-containing film-forming composition is generated and then introduced into the reaction chamber containing the substrate. Temperature of temperature and pressure as well as the substrate in the reaction chamber is maintained under appropriate conditions to at least a portion of deposition of Shiriruami de-containing precursor onto a substrate. In other words, after introducing the evaporated composition into the reaction chamber, the conditions in the reaction chamber are adjusted so that at least a portion of the precursor is precipitated on the substrate to form a Co-containing layer. Those skilled in the art will recognize that "at least a portion of the precursor precipitates" means that some or all of the precursors react with or adhere to the substrate. As used herein, the reactants may be used to aid in the formation of Co-containing layers.

Reaction chambers include, but are not limited to, precipitation methods such as parallel plate reactors, cold wall reactors, hot wall reactors, single wafer reactors, multi-wafer reactors or other such types of precipitation systems. It may be the enclosure or chamber of any of the devices to be executed. All these exemplary reaction chambers can be used as ALD or CVD reaction chambers. The reaction chamber may be maintained at a pressure in the range of about 0.5 milittle to about 20 torr for all ALD and low atmospheric pressure CVD. The low atmospheric pressure CVD and atmospheric pressure CVD pressures may be in the range up to 760 torr (atmospheric pressure). In addition, the temperature in the reaction chamber may be in the range of about 20 ° C to about 600 ° C. Those of skill in the art will recognize that the temperature can be optimized through mere experimentation to achieve the desired results.

The temperature of the reactor can be controlled by controlling the temperature of the substrate holder or by controlling the temperature of the reactor wall. Devices used to heat the substrate are known in the art. The reactor wall is heated at a sufficient growth rate and to a temperature sufficient to obtain the desired film of the desired physical condition and composition. Non-limiting exemplary temperature ranges in which the reactor wall can be heated include from about 20 ° C to about 600 ° C. When the plasma precipitation process is utilized, the precipitation temperature may be in the range of about 20 ° C to about 550 ° C. Alternatively, if a thermal process is performed, the precipitation temperature may range from about 300 ° C to about 600 ° C.

Alternatively, the substrate may be heated at a sufficient growth rate and to a temperature sufficient to obtain the desired cobalt-containing film of the desired physical condition and composition. Non-limiting exemplary temperature ranges in which the substrate can be heated include from about 150 ° C to about 600 ° C. Preferably, the temperature of the substrate is maintained below 500 ° C.

The reactor contains one or more substrates from which the film will be deposited. Hypokeimenon is generally defined as the material on which the process is carried out. The substrate may be any suitable substrate used in semiconductor, photovoltaic, flat panel or LCD-TFT device manufacturing. Examples of suitable substrates include wafers such as silicon, silica, glass or GaAs wafers. The wafer may have one or more layers of different materials precipitated from previous manufacturing steps on it. For example, the wafer may include a silicon layer (crystalline, amorphous, porous, etc.), a silicon oxide layer, a silicon nitride layer, a silicon nitride layer, a carbon-doped silicon oxide (SiCOH) layer, or a combination thereof. .. Further, the wafer may include a copper layer or a noble metal layer (eg, platinum, palladium, rhodium or gold). This layer is an oxide used as a dielectric material in MIM, DRAM or FeRam technology (eg, ZrO _2- based material, HfO _2- based material, TiO _2- based material, rare earth oxide-based material, strontium oxide. A ternary oxide-based material such as ruthenium [SRO]) or a nitride-based film (eg, TaN) used as an oxygen barrier between copper and the low k layer may be included. The wafer may include a barrier layer such as manganese or manganese oxide. Plastic layers such as poly (3,4-ethylenedioxythiophene) poly (styrene sulfonate) [PEDOT: PSS] may also be used. This layer may be flat or patterned. For example, this layer may be a patterned photoresist film made from _{carbon hydride, eg, CH x where x is greater than zero.}

The disclosed process may deposit a cobalt-containing layer directly on the wafer or directly on one or more of the layers on top of the wafer (if the patterned layer forms a substrate). The substrate may be patterned to include vias or trenches with a high aspect ratio. For example, a _{conformal Co-containing film such as CoSi 2} can be deposited using any ALD technique on a through silicon via (TSV) having an aspect ratio in the range of about 20: 1 to about 100: 1. .. In addition, one of ordinary skill in the art will appreciate that the term "film" or "layer" as used herein means the thickness of some material placed or distributed on a surface, and the surface is trenched or You will recognize that it can be a line. Throughout the specification and claims, the wafer and any related layers on it are referred to as substrates. However, in many cases, the preferred substrate utilized may be selected from carbon-doped SiO ₂ , TaN, Ta, TiN, Ru and Si-type substrates such as polysilicon or crystalline silicon substrates.

The disclosed Co-containing film-forming compositions include toluene, ethylbenzene, xylene, mesitylene, decane, dodecane, octane, hexane, pentane, tertiary amines, acetone, tetrahydrofuran, ethanol, ethylmethyl ketone, 1,4-dioxane, Alternatively, it may further contain a solvent such as others. The disclosed compositions can be present in various concentrations in a solvent. For example, the resulting concentration may range from about 0.05M to about 2M.

The Co-containing film-forming composition can be delivered to the reactor or vapor deposition chamber by the Co-containing film-forming composition delivery device of FIGS. 1-3 showing three exemplary embodiments of the Co-containing film-forming composition delivery device.

FIG. 1 is a side view of an embodiment of a Co-containing film-forming composition reactant delivery device 1. In FIG. 1, the disclosed Co-containing film-forming composition 11 is contained in a container 2 having two conduits, an inlet conduit 3 and an outlet conduit 4. Those skilled in the art of reactants will recognize that the vessel 2, inlet conduit 3 and outlet conduit 4 are manufactured to prevent leakage of the gaseous form of the Co-containing film-forming composition 11 even at high temperatures and pressures. ..

The outlet conduit 4 of the delivery device 1 fluidly connects to the reactor (not shown) or to other components between the delivery device and the reactor, such as a gas cabinet, via valve 7. Preferably, the container 2, inlet conduit 3, valve 6, outlet conduit 4 and valve 7 are made of 316L EP or 304 stainless steel. However, those skilled in the art will recognize that other non-reactive materials may also be used in the teachings herein.

In FIG. 1, the end 8 of the inlet conduit 3 is located on the surface of the Co-containing film-forming composition 11, whereas the end 9 of the outlet conduit 4 is on the surface of the Co-containing film-forming composition 11. Located below. In this embodiment, the Co-containing film-forming composition 11 is preferably in liquid form. An inert gas containing, but not limited to, nitrogen, argon, helium and a mixture thereof may be introduced into the inlet conduit 3. The inert gas pressurizes the delivery device 2 so that the liquid Co-containing film-forming composition 11 is forced through the outlet conduit 4 and into the reactor (not shown). The reactor provides the liquid Co-containing film-forming composition 11 with or without the use of a carrier gas such as helium, argon, nitrogen or a mixture thereof to deliver the vapor to the substrate on which the film will be formed. It may include an evaporator that converts it into steam. Alternatively, the liquid Co-containing film-forming composition 10 may be delivered directly to the wafer surface as a jet or aerosol.

FIG. 2 is a side view of a second embodiment of the Co-containing film forming composition delivery device 1. In FIG. 2, the end 8 of the inlet conduit 3 is located below the surface of the Co-containing film-forming composition 11, whereas the end 9 of the outlet conduit 4 is the surface of the Co-containing film-forming composition 11. Located on top of. FIG. 2 also includes any heating element 14 capable of increasing the temperature of the Co-containing film forming composition 11. In this embodiment, the Co-containing film-forming composition 11 can be in solid or liquid form. An inert gas containing, but not limited to, nitrogen, argon, helium and a mixture thereof is introduced into the inlet conduit 3. The inert gas is bubbled through the Co-containing film-forming composition 11, and the mixture of the inert gas and the evaporated Co-containing film-forming composition 11 is carried to the outlet conduit 4 and onto the reactor. Bubbling with a carrier gas can also remove any dissolved oxygen present in the Co-containing film-forming composition.

1 and 2 include valves 6 and 7. Those skilled in the art will recognize that valves 6 and 7 can be placed in open or closed positions for flow through conduits 3 and 4, respectively. A simpler delivery device having a single conduit end on the surface of any of the delivery devices 1 in FIGS. 1 and 2, or any solid or liquid present, is that the Co-containing film-forming composition 11 is in vapor form. It may be used if there is sufficient vapor pressure on the solid / liquid phase. In this case, the Co-containing film-forming composition 11 is delivered in vapor form through the conduit 3 or 4 by simply opening valve 6 in FIG. 1 or valve 7 in FIG. The delivery device 1 can be maintained at a temperature suitable for providing sufficient vapor pressure for the Co-containing film-forming composition 11 to be delivered in vapor form, for example by the use of any heating element 14.

Although FIGS. 1 and 2 disclose two embodiments of the Co-containing film-forming composition delivery device 1, those skilled in the art will appreciate that the inlet and outlet conduits 4 also do not deviate from the disclosure herein. You will recognize that it can be located both above or below the surface of the containing film-forming composition 11. Further, the inlet conduit 3 may be a filling port.

The vapor in solid form of the Co-containing film-forming composition may be delivered to the reactor using a sublimator. FIG. 3 shows an embodiment of an exemplary sublimator 100. The sublimator 100 includes a container 33. The container 33 may be a cylindrical container or may have any shape without limitation. The container 33 is composed of, without limitation, materials such as stainless steel, nickel and alloys thereof, quartz, glass, and other chemically compatible materials. In a particular example, the container 33 is composed of, without limitation, another metal or metal alloy. In certain examples, the container 33 has an inner diameter of about 8 centimeters to about 55 centimeters, or an inner diameter of about 8 centimeters to about 30 centimeters. As will be appreciated by those skilled in the art, different structures may have different dimensions.

The container 33 comprises a sealable top 15, a sealing element 18 and a gasket 20. The sealable upper portion 15 is configured to seal the container 33 from the external environment. The sealable top 15 is configured to allow access to the container 33. In addition, the sealable top 15 is configured for the route of the conduit to the container 33. Instead, the sealable top 15 is configured to allow flow into the container 33. The sealable top 15 is configured to receive and pass through a conduit comprising a dip tube 92 to maintain fluid contact with the container 33. The dip tube 92 having the control valve 90 and the fitting 95 is configured to allow the carrier gas to flow into the container 33. In a particular example, the dip tube 92 extends below the central axis of the container 33. Further, the sealable top 15 is configured to receive and pass through a conduit comprising an outlet tube 12. The carrier gas and the vapor of the Co-containing film-forming composition are removed from the container 33 through the outlet tube 12. The outlet tube 12 includes a control valve 10 and a fitting 5. In a particular example, the outlet tube 12 is fluidly coupled to a gas delivery manifold to conduct the carrier gas from the sublimator 100 to the reactor.

The container 33 and the sealable top 15 are sealed by at least two sealing elements 18; or at least about four sealing elements. In a particular example, the sealable top 15 is sealed to the container 33 by at least about eight sealing elements 18. As will be appreciated by those skilled in the art, the sealing element 18 detachably connects the sealable top 15 to the container 33 and forms a gas resistance seal with the gasket 20. The sealing element 18 may include any suitable means known to those of skill in the art in the technique of sealing container 33. In a particular example, the sealing element 18 comprises a thumbscrew.

As illustrated in FIG. 3, the container 33 further comprises at least one disc disposed therein. The disc will include shelves or horizontal supports for solid materials. In certain embodiments, the internal disc 30 is annularly arranged within the container 33, and the disc 30 includes an outer diameter or outer circumference that is less than the inner or inner circumference of the container 33 to form an opening 31. The outer disc 86 is peripherally arranged within the container 33, and the disc 86 comprises an outer diameter or outer circumference that is, is approximately the same as, or generally matches the inner diameter of the container 33. The external disc 86 forms an opening 87 that is located in the center of the disc. A plurality of discs are arranged in the container 33. The discs are stacked in an alternating fashion, where the internal discs 30, 34, 36, 44 are stacked vertically in the container together with the alternating external discs 62, 78, 82, 86. In an embodiment, the inner discs 30, 34, 36, 44 extend outwardly in an annular shape, and the outer discs 62, 78, 82, 86 extend in an annular shape toward the center of the container 33. As illustrated in the embodiment of FIG. 3, the internal discs 30, 34, 36, 44 do not physically contact the external discs 62, 78, 82, 86.

The assembled sublimator 100 comprises internal disks 30, 34, 36, comprising an aligned and connected support leg 50, an internal path 51, concentric walls 40, 41, 42 and concentric slots 47, 48, 49. 44 is included. The internal discs 30, 34, 36, 44 are stacked vertically and oriented cyclically with respect to the dip tube 92. In addition, the sublimator comprises external disks 62, 78, 82, 86. As illustrated in FIG. 3, the external discs 62, 78, 82, 86 are firmly contained in the vessel 33 for good contact to conduct heat from the vessel 33 to the discs 62, 78, 82, 86. Should be fitted. Preferably, the outer discs 62, 78, 82, 86 are connected to or physically in contact with the inner wall of the container 33.

As illustrated, the external discs 62, 78, 82, 86 and the internal discs 30, 34, 36, 44 are laminated inside the container 33. When assembled in the container 33 to form the sublimator 100, the internal discs 30, 34, 36, 44 are assembled between the assembled external discs 62, 78, 82, 86 and the external gas paths 31, 35, 37, 45. To form. Further, the outer discs 62, 78, 82, 86 form the internal gas paths 56, 79, 83, 87 together with the support legs of the inner discs 30, 34, 36, 44. The walls 40, 41, 42 of the internal disks 30, 34, 36, 44 form grooved slots for holding the solid precursor. The external disks 62, 78, 82, 86 include walls 68, 69, 70 for holding the solid precursor. During assembly, the solid precursor is loaded into the annular slots 47, 48, 49 of the inner disks 30, 34, 36, 44 and the annular slots 64, 65, 66 of the outer disks 62, 78, 82, 86.

Solid powders and / or granular particles with a diameter of less than about 1 centimeter, or less than about 0.5 centimeters, or less than about 0.1 centimeters, are annular slots 47, 48 of internal disks 30, 34, 36, 44. , 49 and the annular slots 64, 65, 66 of the external disks 62, 78, 82, 86. The solid precursor is loaded into the ring-shaped slot of each disc by any method suitable for the uniform distribution of solids in the annular slot. Suitable methods include, but are not limited to, direct injection, use of scoops, use of funnels, automated measurement delivery and pressurized delivery. Depending on the chemistry of the solid precursor material, the loading may be performed in a sealing environment. In addition, the inert gas atmosphere and / or pressurization in the sealing box may be performed for their toxic, volatile, oxidizable, and / or air-sensitive solids. After setting the discs in the container 33, each disc can be loaded. A more preferred procedure is to load the solid before setting the disc into the container 33. The total weight of the solid precursor loaded on the sublimator may be recorded by weighing the sublimator before and after the loading process. In addition, the solid precursor consumed may be calculated by weighing the sublimator after the evaporation and precipitation process.

The dip tube 92 with the control valve 90 and fitting 95 is located in the central path 51 of the aligned and connected support legs of the internal discs 30, 34, 36, 44. Therefore, the dip tube 92 passes through the internal path 51 perpendicularly to the bottom 58 of the container 33. The end 55 of the dip tube is located proximal to the bottom 58 of the container / or on the gas window 52. The gas window 52 is arranged on the bottom internal disk 44. The gas window 52 is configured to allow the carrier gas to flow from the dip tube 92. In the assembled sublimator 100, the gas path 59 is formed by the bottom surface 58 of the container 33 and the bottom internal disk 44. In a particular example, the gas pathway 59 is configured to heat the carrier gas.

During operation, the carrier gas is preheated before being introduced into the vessel 33 via the dip tube 92. Alternatively, the carrier gas can be heated while it passes through the gas path 59 by the bottom surface 58. The bottom surface 58 is thermally connected and / or heated by an external heater, consistent with the teachings herein. The carrier gas then passes through the gas path 45 formed by the outer wall 42 of the inner disk 44 and the outer wall 61 of the outer disk 62. The gas path 45 is led to the top of the internal disk 44. The carrier gas continuously flows over the top of the solid precursor loaded in the annular slots 47, 48 and 49. The sublimated solid vapor from the annular slots 47, 48, 49 is mixed with the carrier gas and flows vertically upward through the vessel 33.

FIG. 3 discloses an embodiment of a sublimator capable of delivering any vapor of a solid Co-containing film-forming composition to a reactor, but those skilled in the art will not deviate from the teachings herein. , You will recognize that other sublimator designs may also be appropriate. Ultimately, one of ordinary skill in the art will appreciate that the disclosed Co-containing film-forming composition does not deviate from the teachings herein, such as the ampoules disclosed in WO 2006/059187 to Jurkik et al. You will recognize that it can be delivered to semiconductor processing tools using the delivery device of.

If desired, the Co-containing film-forming composition device of FIGS. 1-3 may be heated to a temperature at which the Co-containing film-forming composition is in its liquid phase and is capable of having sufficient vapor pressure. good. The delivery device may be maintained at a temperature in the range 0-150 ° C, for example. Those skilled in the art will recognize that the temperature of the delivery device can be adjusted in a well-known manner to control the amount of Co-containing film-forming composition that evaporates.

In addition to the disclosed precursors, reactants may also be introduced into the reactor. The reactants are O ₂ , O ₃
, _H 2 _O, oxygen, such as one of the H _{2 O} 2; _O ^· or OH ^· which any oxygen containing radical; formic acid, acetic acid, carboxylic acids such as propionic acid, NO, radical species of NO ₂ or carboxylic acid; para It may contain formaldehyde; and mixtures thereof. Preferably, the oxygen-containing reactant is selected from the group consisting of its oxygen-containing radicals such as _{O 2} , O ₃ , H ₂ O, H ₂ O ₂ , O ^· or OH ^{·, and mixtures thereof.} Preferably, when the ALD process is performed, the reactant is plasma treated oxygen, ozone or a combination thereof. If an oxygen-containing reactant is used, the resulting cobalt-containing film will also contain oxygen.

Instead, the reactants are H ₂ , NH ₃ , (SiH ₃ ) ₃ N, hydride silanes (eg SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ , Si ₅ H ₁₀ , Si _6). H _12), chlorosilane and chloropolysilane _{(e.g., SiHCl 3, SiH 2 Cl 2} , S i H 3 Cl, Si 2 Cl 6, Si 2 HCl 5, Si 3 Cl 8), alkyl silanes (eg, _(CH 3) _{2 SiH 2, (C 2 H} 5) 2 SiH 2, (CH 3) SiH 3, (C 2 H 5) SiH 3), hydrazine _{(e.g., N 2 H4, MeHNNH 2,} MeHNNHMe), organic amines (e.g., N (CH ₃ ) H ₂ , N (C ₂ H ₅ ) H ₂ , N (CH ₃ ) ₂ H, N (C ₂ H ₅ ) ₂ H, N (CH ₃ ) ₃ , N (C ₂ H ₅ ) _3, (SiMe _{3) 2} NH), pyrazoline, pyridine, B-containing molecules _(e.g., B ₂ H 6, 9-borabicyclo [3,3,1] nonane, Torimechirubo Ron, triethyl boron, borazine), alkali metal (e.g. , Trimethylaluminum, triethylaluminum, dimethylzinc, diethylzinc), alcohols (eg, ethanol or methanol), radical species thereof and mixtures thereof. Preferably, the reactants are H ₂ , NH ₃ , SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , SiH ₂ Me ₂ , SiH ₂ Et ₂ , N (SiH ₃ ) ₃ , ethanol, hydrogen radicals thereof and their hydrogen radicals thereof. It is a mixture. Preferably, the reactants are SiHCI ₃ , Si ₂ CI ₆ , Si ₂ HCI ₅ , Si ₂ H ₂ CI ₄ and Cyclo- _{Si 6} H ₆ CI ₆ . When these reactants are used, the resulting Co-containing film can be pure Co.

The reactants may be treated with a plasma to decompose the reactants into their radical form. When treated with plasma, N ₂ may also be used as a reactant. For example, the plasma can be generated at an output in the range of about 50 W to about 500 W, preferably about 100 W to about 200 W. The plasma can be generated or it can exist in the reactor itself. Instead, the plasma can generally be present at a location removed from the reactor, such as the distal plasma system. Those skilled in the art will recognize suitable methods and equipment for such plasma processing.

The disclosed Co-containing film-forming compositions are used with halosilanes or polyhalodisilanes such as hexachlorodisilane, pentachlorodisilane or tetrachlorodisilane, and one or more reactants to be used with CoSi, CoSiCN or CoSiCOH. A film may be formed.

Preferably Co-containing film, for example, without limitation, Ti, Mn, Ta, Hf , Nb, Mg, Al, Sr, Y, Ba, Ca, As, Sb, Bi, Sn, Pb, Koh Roh id (Er etc. ) Or a combination thereof, the reactants are selected from, but not limited to _{, alkyls such as Ln (RCp) 3} , alkylamines such as Ti ( _{NET 2} ) _4, or any combination thereof. Can include other precursors.

The Co-containing film-forming composition and one or more reactants can be introduced into the reaction chamber simultaneously (eg, CVD), over time (eg, ALD) or in other combinations. For example, the Co-containing film-forming composition can be introduced in one pulse, and two additional reactants can be introduced together in another pulse (eg, modified ALD). Alternatively, the reaction chamber may already contain the reactants prior to the introduction of the Co-containing film-forming composition. The reactants may pass through a plasma system locally or distally from the reaction chamber and be decomposed into radicals. Alternatively, the Co-containing film-forming composition may be continuously introduced into the reaction chamber (eg, pulse CVD), although the other reactants are introduced by pulse. In each example, the pulse may be followed by a purge or exhaust step to remove the excess amount of introduced components. In each example, the pulse may last for a period ranging from about 0.01 seconds to about 10 seconds, or about 0.3 seconds to about 3 seconds, or about 0.5 seconds to about 2 seconds. In another option, the Co-containing film-forming composition and one or more reactants may be simultaneously sprayed from a shower head under which a susceptor holding several wafers is spun (eg, space). ALD).

In one non-limiting exemplary ALD type process, the vapor phase of the Co-containing film-forming composition is introduced into the reaction chamber, and where, at least a portion of Shiriruami de-containing precursor, Si, SiO _2, It reacts with a suitable substrate such as Al ₂ O _{3 to form an adsorbed cobalt layer.} The excess composition can then be removed from the reaction chamber by purging and / or evacuating the reaction chamber. An oxygen source is introduced into the reaction chamber, where it reacts with the adsorbed cobalt layer in a self-limiting manner. Any excess oxygen source is removed from the reaction chamber by purging and / or evacuating the reaction chamber. If the desired film is a cobalt oxide film, this two-step process may be repeated until the desired film thickness can be provided or a film with the required thickness is obtained.

Alternatively, if the desired film contains a second element (ie, x can be 1-4 and M is Ti, Ta, Hf, Nb, Mg, Al, Sr, Y, Ba, Ca, As, Sb, Bi, Sn, Pb, Koh Roh id (Er) or CoMn _x) a combination thereof, after the above 2-step process, the second introduction of the vapor of the precursor run into the reaction chamber May be done. The second precursor will be selected based on the nature of the film being deposited. After introduction into the reaction chamber, the second precursor contacts the substrate. Any excess of the second precursor is removed from the reaction chamber by purging and / or evacuating the reaction chamber. Again, an N source may be introduced into the reaction chamber to react with the second precursor. Excess N sources are removed from the reaction chamber by purging and / or evacuating the reaction chamber. Once the desired film thickness is achieved, the process may be terminated. However, if a thicker film is desired, the entire 4-step process may be repeated. By substituting the supply of the Co-containing film-forming composition, the second precursor and the N source, a film of the desired composition and thickness can be precipitated.

Further, by changing the number of pulses, a film having a desired stoichiometric M: Co ratio can be obtained. For example, CoMn film, as in each pulse is the pulse of the NH ₃ source followed may be obtained by having a second precursor of one pulse of the Co-containing film-forming composition and 1 pulse. However, those skilled in the art will recognize that the number of pulses required to obtain the desired film cannot be the same as the stoichiometric ratio of the resulting film.

The cobalt-containing films resulting from the processes discussed above are Co, CoSi ₂ , CoO ₂ , CoN, CoMN, CoC, CoON, CoCN, CoCON or MCoO _x (where M is Hf, Zr, Ti, in the formula). It is an element such as Nb, Ta or Ge, and x can be 0-4 depending on the oxidation state of M). Those skilled in the art will recognize that the desired film composition can be obtained with a fair selection of suitable Co-containing film-forming compositions and reactants.

Once the desired film thickness is obtained, the film may undergo additional processes such as thermal annealing, combustion chamber annealing, rapid thermal annealing, UV or e-beam curing and / or plasma gas exposure. One of ordinary skill in the art will be aware of the systems and methods used to perform these additional process steps. For example, the cobalt-containing film is prepared at about 200 ° C. to about 1000 ° C. for a period of about 0.1 seconds to about 7200 seconds under an inert atmosphere, an H-containing atmosphere, an N-containing atmosphere, an O-containing atmosphere or a combination thereof. It may be exposed to a range of temperatures. Most preferably, the temperature is 600 ° C. for less than 3600 seconds under an H-containing atmosphere. The resulting film may contain less impurities and therefore may have improved performance characteristics. The annealing step may be performed in the same reaction chamber in which the precipitation process is performed. Alternatively, the substrate may be removed from the reaction chamber and the annealing / flash annealing process may be performed in a separate device. All of the above post-treatment methods have been found to be particularly effective in reducing carbon and nitrogen contamination of cobalt-containing films.

The following non-limiting examples are provided to further illustrate embodiments of the present invention. However, the examples are not intended to be inclusive and are not intended to limit the scope of the invention described herein.

Example 1: Synthesis of Co [N (SiMe ₃ ) ₂ ] ₂ (THF) Flasks _{were filled with CoCl 2} (7.08 g) and THF (50 ml). A NaN (SiMe ₃ ) ₂ THF solution (100 mL) was added dropwise at −78 ° C., then the mixture was warmed to room temperature (about 23 ° C., RT). After an overnight reaction at room temperature, the solution was filtered through Celite ™ brand diatomaceous earth and all solvents were removed under reduced pressure. The light green compound was purified by sublimation under reduced pressure (50 milittle, 70-80 ° C.). Yield 58%. The product was recrystallized from hexane at −30 ° C. for XRD analysis. Air-sensitive young grass-colored crystals were obtained.
^{1 1} H NMR (δ, C ₆ D ₆ ) -16.98 (s) 96.91 (brs), DSC 58 ° C (melting point), 183 ° C (decomposition), vapor pressure 108 ° C, 1 torr.

Example 2: Synthesis of Co [N (SiMe ₂ Et) ₂ ] ₂ (THF) Flasks were filled with _{CoCl 2 and THF.} A NaN (SiMe ₂ Et) ₂ THF solution was added dropwise at −78 ° C., then the mixture was warmed to room temperature (about 23 ° C., RT). A dark green liquid was obtained.
^{1 1} H NMR (δ, C ₆ D ₆ ) -34.69 (s), -19.67 (s) 2.11 (brs) 89.12 (brs), DSC 215 ° C (decomposition), vapor pressure 100 ° C 1 torr.

Example 3: Synthesis of Co [N (SiMe ₃ ) ₂ ] ₂ (adduct) 10 equal amounts of adduct ligand (dried pyridine (py.), Dimethylethylamine, diethylmethylamine, triethylamine, 1-methyl- _{Pyrrolidine) was added dropwise to a hexane solution (5 mL) of Co [N (SiMe 3} ) ₂ ] ₂ (THF) (1.0 g) prepared in the same manner as in Example 1 under nitrogen. After the overnight reaction, the solvent and excess adduct ligand were removed under reduced pressure. The crude product was extracted with dry hexane and filtered through a PTFE filter. The target compound was purified by recrystallization from dry hexane at −30 ° C. and dried at room temperature under reduced pressure. Each addition compound was isolated as a blue to green solid. Ppyridine adduct (light blue, 78% yield), dimethylethylamine adduct (blue, 87% yield), diethylmethylamine adduct (dark green, 56% yield), triethylamine adduct (dark green, 93% yield) %), 1-Methyl-pyrrolidin adduct (light blue, yield 86%).

Characterizing additional compounds: Each compound ^{was analyzed by 1} H NMR and XRD.
Py adduct: ^{1 1} H NMR (δ, C ₆ D ₆ ) -18.84 (s) 67.04 (brs), 138.66 (brs), DSC 100 ° C (mp), 216 ° C (dec) ), 1 torr at vapor pressure of 153 ° C.
Dimethylethylamine adduct ^{1 1} H NMR (δ, C ₆ D ₆ ) -24.91 (s) 71.77 (brs), DSC 88 ° C. (mp), 203 ° C. (dec), vapor pressure 88 ° C. 1 torr.
Diethylmethylamine adduct ^{1 1} H NMR (δ, C ₆ D ₆ ) -22.58 (brs), 59.40 (brs), 97.71 (brs) DSC 90 ° C (mp), 210 ° C ( dec), 1 torr at a vapor pressure of 82 ° C.
Triethylamine adduct ^{1 1} H NMR (δ, C ₆ D ₆ ) -17.01 (s), 96.68 (brs), DSC 221 ° C. (dec), vapor pressure 100 ° C., 1 torr.
1-Methyl-pyrrolidin adduct ^{1 1} H NMR (δ, C ₆ D ₆ )-25.07 (s), 62.06 (brs), 76.22 (brs), DSC 148 ° C. (mp), 1 torr at 210 ° C. (dec) and vapor pressure 114 ° C.

Example 4: Synthesis of Co [N (SiMe ₂ Et) ₂ ] _{2 (dimethylethylamine) Co [N (SiMe 2} Et) ₂ prepared in the same manner as in Example 2 under nitrogen in an amount of 10 equal amounts of dimethylethylamine. ] ₂ (THF) (1.0 g) was added dropwise to a hexane solution (5 mL). After the overnight reaction, the solvent and excess adduct ligand were removed under reduced pressure. The crude product was extracted with dry hexane and filtered through a PTFE filter. The target compound was purified by distillation under reduced pressure (30 milittle). A dark green liquid was obtained (yield 45%).
^{1 1} H NMR (δ, C ₆ D ₆ )-20.45 (brs), -16.20 (s), 0.07 (s) 0.50 (q, J = 8Hz), 0.96 (t, J = 8 Hz), 12.75 (brs) 94.02 (brs). 1 torr at DSC 124 ° C. (dec) and vapor pressure 124 ° C.

Example 5: Thermal analysis Under nitrogen (220 sccm), volatility was monitored by TGA (thermogravimetric analysis, METTLER, TGA / SDTA851). The temperature was increased at 10 ° C./min. Test samples were prepared in an aluminum pan under nitrogen. The results are shown in FIGS. 4 and 5.

FIG. 4 is a comparative open cup TGA graph of Co [N (SiR ¹ R ² R ³ ) ₂ ] _{2 (adduct) precursors measured at 1010 mbar.} 1010 millibars is equal to atmospheric pressure, or pressure close to the pressure at which the precursor can be stored, or equal to the pressure at which the precursor can be stored.

As can be seen in FIG. 4, Co [N (SiMe ₃ ) ₂ ] ₂ (NMe ₂ Et) shows an evaporation close to 100%, and Co [N (SiMe ₃ ) ₂ ] ₂ (NET ₃ ). Leaves almost no residue. Co [N (SiMe ₃ ) ₂ ] ₂ (Me-pyrrolidine), Co [N (SiMe ₃ ) ₂ ] ₂ (NMeEt ₂ ) and Co [N (SiMe ₃ ) ₂ ] ₂ (THF) are all about 5 to 5 Leave a 10% residue. Both Co [N (SiMe ₂ Et) ₂ ] ₂ (THF) and Co [N (SiMe ₃ ) ₂ ] ₂ (py) leave about 10% residue. Co [N (SiMe ₂ Et) ₂ ] ₂ (NMe ₂ Et) leaves a residue of more than 20%.

FIG. 5 is a comparative open cup TGA graph of Co [N (SiR ¹ R ² R ³ ) ₂ ] _{2 (adduct) precursors measured at 20 millibars.} 20 millibars represents a pressure close to the pressure at which the precursor can be used, or the pressure at which the precursor can be used.

As can be seen in FIG. 5, all six tested precursors (ie, Co [N (SiMe ₂ Et) ₂ ] ₂ (THF), Co [N (SiMe ₃ ) ₂ ] ₂ (py)). , Co [N (SiMe ₃ ) ₂ ] ₂ (NMeEt ₂ ), Co [N (SiMe ₃ ) ₂ ] ₂ (NEt ₃ ), Co [N (SiMe ₃ ) ₂ ] ₂ (Me-pyrrolidin) and Co [N (SiMe ₂ Et) ₂ ] ₂ (NMe ₂ Et) leaves a residue close to 0%.

As demonstrated in FIGS. 4 and 5, the Co [N (SiR ¹ R ² R ³ ) ₂ ] ₂ (adduct) precursor line exhibits similar properties despite structural similarities of the precursors. No.

With respect to precursor selection, volatility is important for delivery to the reaction chamber. TGA data in the atmosphere show which precursors are suitable for use and which precursors are unsuitable for use. Preferably, the precursor exhibits clear evaporation under reduced pressure.

Example 6: Thermal stress test The sample was heated at a temperature corresponding to the vapor pressure of 1 torr for 2 weeks to 3 months. Figures 6-10 show TGA graphs performed at 1010 millibar (atmospheric pressure) showing any changes over a particular time period for a sample maintained at a particular temperature. FIG. 6 shows the results of Co [N (SiMe ₃ ) ₂ ] ₂ (py) at 150 ° C. for 0 and 1 week. FIG. 7 shows the results _{of Co [N (SiMe 3} ) ₂ ] ₂ (NMe ₂ Et) at 90 ° C. for 0; 1, 2 and 3 weeks and 1 and 2 months. FIG. 8 shows the results _{of Co [N (SiMe 3} ) ₂ ] ₂ (NET ₂ Me) at 80 ° C. for 0, 1, 2 and 3 weeks. FIG. 9 _{shows the results of Co [N (SiMe 3} ) ₂ ] ₂ (1-Me-pyrrolidin) at 110 ° C. for 0, 1 and 2 weeks. FIG. 10 shows the results _{of Co [N (SiMe 2} Et) ₂ ] ₂ (NMe ₂ Et) at 120 ° C. for 0, 1 and 2 weeks.

Precursor stability at operating temperature is also important. If precursors are used, heat the canister to produce sufficient steam, at least 1 torr. The canister may be heated above 1 torr temperature to produce a high growth rate. Therefore, the precursor must be stable without degradation in order to retain the expected vapor delivery.

Materials used in the semiconductor industry due to low vapor pressure, such as these compounds, must remain stable at high temperatures. The high temperature is one torr (133 Pa) of steam / partial pressure in the canister, as this pressure has been found to be sufficient to provide the proper supply of material through the distribution system and into the process chamber. Selected to provide precursor pressure. The canister can be kept at a high temperature for an extended period of time (eg, weeks or months) corresponding to the usage rate / productivity of the process tool. At such high temperatures, materials that do not retain their characteristics cannot be effectively utilized as precursors for semiconductor processes without additional exceptional equipment or conditioning. Applicant has surprisingly found that, Co _(TMSA) NEtMe ₂ adduct of ₂ precursor was found to have excellent thermal properties after prolonged exposure to high temperature.

Material stability does not depend solely on the volatility of the adduct. NEtMe ₂ adduct has a higher volatility than _NEt 2 Me adduct (see FIG. 4) show significant degradation after 3 weeks. In addition, it can be useful in the precipitation of pure Co films, as the precursor does not contain oxygen.

_{Applicants have holes with an aspect ratio of NEtMe 2 in} the range of 3: 1 to 50: 1, preferably 5: 1 to 10: 1, because the precursor will not exhibit degradation of similar precursors. And believe that it will allow conformal step coating in trenches. The applicant also considers that the NEtMe ₂ precursor will provide a consistent precipitation of face-centered cubic cobalt nitride (Co4N). Co4N provides a strong adhesive reinforcement layer between the TaN or WN and the copper seed layer in a copper damask structure.

To illustrate the nature of the invention, many additional changes in the arrangement of details, materials, steps and parts described and exemplified herein are specified in the appended claims. It will be appreciated that within the principles and scope of the above, it can be carried out by those skilled in the art. Therefore, the present invention is not intended to be limited to the particular embodiments and / or accompanying drawings in the above examples.

Claims (14)

A method of precipitating a Co-containing layer on a substrate, which is a method of precipitating a Co-containing layer.
Co-containing film-forming composition comprising a silylamide-containing precursor selected from Co [N (SiMe ₃ ) ₂ ] ₂ (NMe ₂ Et), Co [N (SiMe ₃ ) ₂ ] ₂ (NMeEt _{2) or a combination thereof.} Introducing the vapor of an object into a reactor in which a substrate is placed,
A method comprising depositing at least a part of the silylamide-containing precursor on the substrate to form the Co-containing layer using a thin-film deposition method. The method of claim 1, wherein the silylamide-containing precursor is Co [N (SiMe ₃ ) ₂ ] ₂ (NMe _{2 Et).} The method according to claim 1, wherein the silylamide-containing precursor is Co [N (SiMe ₃ ) ₂ ] ₂ (NMeEt _2). The method according to any one of claims 1 to 3, wherein the Co-containing layer is Co. The method according to any one of claims 1 to 3, wherein the Co-containing layer is CoSi _2. The method according to claim 4 or 5, wherein the substrate is SiO _2. The method according to claim 5, wherein the substrate is Si. A method of precipitating a Co-containing layer on a substrate, which is a method of precipitating a Co-containing layer.
Co-containing film-forming composition comprising a silylamide-containing precursor selected from Co [N (SiMe ₃ ) ₂ ] ₂ (NMe ₂ Et), Co [N (SiMe ₃ ) ₂ ] ₂ (NMeEt _{2) or a combination thereof.} A Co-containing film-forming composition delivery device comprising a substance is fluidly connected to a vapor deposition chamber, and
The Co-containing film-forming composition delivery device is heated to a temperature of about 0.2 torr (about 27 Pascals) to about 1.5 torr (about 200 Pascals) to generate a vapor pressure of the Co-containing film-forming composition. And;
The vapor of the Co-containing film-forming composition is delivered into the vapor deposition chamber in which the substrate is arranged.
A method comprising depositing at least a part of the silylamide-containing precursor on the substrate to form the Co-containing layer using a thin-film deposition method. The method of claim 8, further comprising maintaining the Co-containing film-forming composition delivery device at the temperature for a period of 2 weeks to 12 months. The method according to claim 8 or 9, wherein the silylamide-containing precursor is Co [N (SiMe ₃ ) ₂ ] ₂ (NMe _{2 Et).} Containing a silylamide-containing precursor selected from Co [N (SiMe ₃ ) ₂ ] ₂ (NMe ₂ Et), Co [N (SiMe ₃ ) ₂ ] ₂ (NMeEt ₂ ) or a combination thereof, and at 80 ° C. A cobalt-containing film-forming composition having thermal stability demonstrated by thermogravimetric analysis with a residual mass of less than 5% after 2 weeks. The silylamide-containing precursor is Co [N (SiMe ₃ ) ₂ ] ₂ (NMe ₂ Et) and has thermal stability demonstrated by thermogravimetric analysis with a residual mass of less than 5% after 2 months at 90 ° C. The cobalt-containing film-forming composition according to claim 11. The Co-containing film-forming composition is a silylamide-containing precursor selected from _{Co [N (SiMe 3} ) ₂ ] ₂ (NMe ₂ Et), Co [N (SiMe ₃ ) ₂ ] ₂ (NMeEt _{2), or a combination thereof.} The cobalt-containing film-forming composition according to claim 11 , which is essentially composed of. The cobalt-containing film-forming composition according to claim 11 , wherein the Co-containing film-forming composition is essentially composed of _{Co [N (SiMe 3} ) ₂ ] ₂ (NMe _{2 Et).}

Images